Bicyclic ketones having biological activity

ABSTRACT

Bicyclic ketones of the formula   WHEREIN R1, R2, R3, R4, X1, X2, X3, X4 and X5 are certain substituents selected from hydrogen, halogen, alkyl, alkenyl, halogenated alkyl, halogenated alkenyl, alkoxy, hydrocarbyl, halogen-substituted hydrocarbyl, carboxy, hydroxy-substituted alkyl, alkoxy-substituted alkyl, and hydroxy-substituted alkoxyalkyl, with at least two of X1, X2, X3 and X4 being halogen, and X6 is halogen. The bicyclic ketones are made by treating a corresponding tricyclic hemiketal with phosphorus halide and hydrolyzing. The bicyclic ketones are useful as chemical intermediates and as insecticides.

United States Patent 1191 Hoch BICYCLIC KETONES HAVING BIOLOGICALACTIVITY Inventor: Paul E. Hoch, Moraga, Calif.

Assignee: Hooker Chemical Corporation, Niagara Falls, NY.

Filed: Apr. 30, 1971 Appl. No.: 139,254

Iilaid fis."Aiifiitioii fiaiaf This Application is a Div. of Ser. No.714,058, Mar. 18, 1969, Pat. No. 3,661,998, which is acontinuationin-part of application Ser. No. 413,952, Nov. 24, 1964,abandoned.

US. Cl. 260/586 R, 260/590, 260/617 R, v 260/618 D, 260/618 R, 260/346.1R, 260/347.2, 260/347.8, 424/331, 424/332 Int. Cl. C07c 49/27, C07c49/80 Field of Search 260/587, 590

References Cited UNITED STATES PATENTS l2/l92l Rupe 260/587 10/1936Yasuhiko et al 260/587 10/1953 Buntin 2'60/587 11/1953 Nishimitsu et al.260/587 [11] 3,821,307 1 June 28, 1974 Primary Examiner-Leon ZitverAssistant Examiner-Norman Morgenstern A n-411w F rmP .Cas aaDana dq,

Studley; William J. Crossetta, Jr.

ABSTRACT Bicyclic ketones of the formula wherein R, R R, R, X, X X, Xand X are cerhalogen. The bicyclic ketones are made by treating acorresponding yricyclic hemike'tal with phosphorus halide andhydrolyzing. The. bicyclic ketones are useful as chemical intennediatesand as insecticides.

8 Claims, No Drawings BICYCLIC KETONES HAVING BIOLOGICAL ACTIVITY and toprocess for their preparation. More specifically,

the invention relates to novel'cyclic ketone composi tions, a novelreaction for the production of such compounds, and methods for utilizingthe compositions in the control of pests, and as chemical intermediates.

ln accordance with this invention, there are provided compounds havingthe formula:

wherein X and X are independently selected from the group consisting ofhydrogen, halogen, alkyl, alkenyl,

halogenated alkyl and halogenated alkenyl;

X and X are independently selected from the group consisting ofhydrogen, halogen, alkoxy, alkyl, alkenyl, halogenated alkyl, andhalogenated alkenyl, at least two of X, X X and X are being halogen;

X is selected from the group consisting of hydrogen, halogen and alkoxy;X is halogen; R and R are independently selected from the groupconsisting of hydrogen, hydrocarbyl, halogensubstituted hydrocarbyl, andcarboxy; I R and R are independently selected from the group consistingof hydrogen, hydrocarbyl, halogensubstituted hydrocarbyl,hydroxy-substituted alkyl, alkoxy-substituted alkyl, andhydroxy-substituted alkoxyalkyl; and R and R can join to form acycloalkyl group.

The hydrocarbyl radicals are,monovalent radicals derivable fromahydrocarbon by the removal of one hydrogen atom. Typical hydrocarbylradicals are alkyl, alkenyl, aryl, cycloalkyl and the like, defined withgreater particularity herein. I

Illustrative examples of the alkyl substituents, which usually containfrom 1 to about 18 carbon atoms, and preferably lower alkyl, such asfrom 1 to about 6 carbon atoms, are methyl, ethyl, propyl, isopropyl,butyl,

isobutyl, amyL'hexyl, eyclohexyl, heptyl, octyl, rionyl, dodecyl,pentadecyl, stearyl, octadecyl, and the like, said alkyl group being amonovalent radical derivable from an aliphatic hydrocarbon by theremoval of one hydrogen atom. The alkylene radicals can be similarlydescribed, except that they are divalent radicals derivable from analiphatic hydrocarbon by the removal of two hydrogen atoms, such asmethylene, ethylene, and the like. The alkyl radical can be substitutedby halo gen, such as chlorine, bromine, or fluorine, as in chloromethyl,dichloromethyl, trichloromethyl, trifluoromethyl, bromoethyl,chloroethyl, fluoropropyl, hexachloroisopropyl, chlorobutyl, bromobutyl,chlorocyclohexyl; chloropropyl, bromooctyl, chlorooctyl, chlorodecyl,chlorodedecyl, bromododecyl, bromopentadecyl, and-the like.

Among the alkenyl substituents which usually contain from 1 to about 18carbon atoms, and preferably lower alkenyl, such as from 1 to about 6carbon atoms, are vinyl, allyl, butenyl, hexenyl, octenyl, dodecenyl,and the like, said alkenyl group being a radical derivable from analkene by the removal of one hydrogen atom. The alkenyl radical can besubstituted by halogen, such as chlorine, bromine or fluorine as intrichlorovinyl, 2-chloroallyl, 2,3-difluorobutenyl, 2,3-dichlorododecenyl, 2-bromoallyl, and the like.

Typical aryl substituents including aralkyl and alkaryl groups, whichusually contain from 6 to about 18 carbon atoms, and preferably from 6to about 10 carbon atoms, are phenyl, benzyl, tolyl, .phenylethyl,xylyl, naphthyl, hexylphenyl, and the like, said aryl group being amonovalent radical derivable from an aromatic hydrocarbon by the removalof one hydrogen atom. The aryl radicals can be substituted by halogen,such as chlorine, bromine, and fluorine, as in p-chlorophenyl,p-bromophenyl, p-fluorophenyl, and the like.

Typical cycloalkyl substituents, which usually contain from three toabout twelve carbon atoms, are cyclohexyl, cyclopropyl, cyclopentyl,cycloheptyl, cyclooctyl, and the like, said cycloalkyl group being amonovalent radical derivable from an alicyclic hydrocarbon by theremoval of one hydrogen atom. The cycloalkyl radicals can be substitutedby halogen, e.g., chlorine, bromine and fluorine as in chlorocyclohoxyl,bromocyclopentyl, fluorocyclohexyl, and the like.

The substituting halogen atoms which are useful include chlorine,bromine, and fluorine. The halogenated elkyl, aryl, cycloalkyl oralkenyl radicals can bear from one halogen up to a number, correspondingto perhalogenation, i.e., all hydrogens replaced with halogen atoms.

The preferred compounds of the invention are those wherein the halogensubstituents are chlorine or bromine, and in which R, R and R arehydrogen, and R is selected from hydrogen, and chloro-substituted loweralkyl. Even more preferred are such compounds wherein the halogen ischlorine. V-

The compounds of the invention are prepared in a series of reactionsstarting with selected bicyclic alcohols. These alcohols are prepared byreacting the appropriate substituted cyclopentadiene and unsaturatedalcohol as represented by the following equation.

wherein X and X are independently selected from the group consisting ofhydrogen, halogen, alkyl and alkenyl;.

X and X are independently selected from the group consisting ofhydrogen, halogen, alkoxy, alkyl, and alkenyl, at least two of X, X, X'and X being halogen;

X and X are independently selected from the group consisting ofhydrogen, halogen and alkoxy,

at least one ofX and X being halogen;

R and R are independently selected from the group consisting ofhydrogen, hydrocarbyl, and hydroxy-substituted alkyl;

R and R are independently selected from the group consisting ofhydrogen, hydrocarbyl, hydroxy-substituted alkyl, alkoxy-substitutedalkyl and hydroxy-substituted alkoxy alkyl, and

R and R can join to form a cycloalkyl group, generally of 5 to 6 carbonatoms.

The halogen, hydrocarbyl, alkyl and alkenyl radicals are the same asthose described he'reinbefore. The

preparation of. such alcohols is described in detail in uents arechlorine, fluorine, bromine and mixtures I thereof, preferably chlorine.Suitable alcohols are, for' example, 2-butenyl alcohol; cinnamylalcohol; 1-

.carboxy-3-hy'droxy propene-l; 2-butene-l,4-diol; 3-

1,4-. cyclohexyl-Z-butene 1,4-diol; 3,4-dihydroxy-2 butene;

hexene-2,5-diol; 8-hexadecene-7 l O-diol;

3-hydroxycyclopentene; 4,3-hydroxycyclohexene-l, and the like. Compoundsthat are readily convertible to alcohols in the reaction process arealso useful, such as 3,4-epoxy-l-butane and 3,4-epoxy-l-hexane.

The preparation of the compounds of the invention is illustrated by thefollowing equations wherein the reaction steps are designated by theletter A through C, but is not intended to be limited thereby.

H C1 Hz A H3 3 Ig-CHZOH R 2 H 1 i 1 l I O Hz or H H 01- H, C 01- 41,, i013 HZ H 0 PE.othol In the reaction designated on the chart by A, thebicyclic alcohol is contacted with a strong base in an alcohol or anaqueous alcoholic medium. The strong base is one that is capable offorming an alkoxide with the alcohol medium, such as an alkali metalhydroxide or an alkali metal itself. Suitable alkali reactants are sovcohols or like media for use in forming the alkoxide, or

. As indicated herein, the alcoholic component can be a monohydricalcohol, such as methanol, a polyhydric alcohol, such as ethylene glycoland glycerol, a mercaptan, such as ethyl mercaptan, a polythiol, such asB-mercapto-orthanol, or can bear a combination of hydroxyl and mercaptogroups. The alkali reactant is employed in an amount sufficient toprovide at least three moles of alkali or alkoxide per mole of bicyclicalcohol, and preferably about four, moles per mole are employedA greateramount can be employed, if desired,

' for example up to ten moles per mole. A minimum of at least threemoles of alcoholic component is employed per mole of bicyclic alcohol,but more usually a large excess, for example, up to 100 moles per mole,is employed to supply a solvent for the reaction. Other solvents canalso be employed, such as inert diluents that do not participate in thereaction, but which are solvents for the bicyclic alcohol. Such diluentsare dimethylsulfoxide, tertiary amines, such as N-methyl morpholine, andthe like.

In carrying out Reaction A, thereaction mixture is generally heated toaboutthe reflux temperature, so that the temperature is somewhatdependent on the boiling point of the alcoholic medium. However, thereaction temperature is generally in the range of about 25 to C. Thereaction time can be varied over a considerable extent, but willgenerally be in the range of one to ten hours. At the completion of thereaction, the reaction mixture is acidified with a mineral acid, such ashydrochloric acid, and can be diluted with water, or if desired, thesesteps can be reversed. The reaction mixture is ordinarily filtered toremove inorganic salts, and any excess solvent can be removed from thereaction mixture by distillation. The product of the reaction can bepurified by crystallization, washing, and drying orother suitable means.

Reaction B is generally carried out by suspending the tricyclic ketalproduce to Reaction A in a solution of a mineral acid, such as sulfuricacid, phosphoric acid, hydrogen bromide, hydrogen iodide, hydrochloricacid (in a misible solvent such as acetic acid); metal chlorides, suchas aluminum chloride, zinc chloride, and the like. The concentrated acidsolution are preferably employed. At least about two moles of acid areused per mole of tricyclic ketal, but more usually a large excess, forexample, up to 100 moles per mole is employed to provide a solvent forthe reaction. An inert solvent or co-solvent can also be employed. Thereaction temperature is generally in the range of 50 to 100 degreescentigrade, or up to the reflux temperature of the reaction mixture. Thereaction is facilitated by agitation and the reaction time can vary froma few minutes up to hours, but preferably is in the range of 10 to 60minutes, more preferably 10 to 30 minutes. After the completion of thereaction, the reaction mixture is cooled and filtered to recover theproduct. The resulting product can be purified by recrystallization,washing, drying, and other suitable methods.

In Reaction B, if the tricyclic ketal starting material has an Rsubstituent that is hydroxyl-substituted (as produced in a series ofreactions beginning with a bicyclic diol), somewhat milder reactionconditions are employed to inhibit fonnation of a tricyclic ketonerather than the indicated product of Reaction B. Under thesecircumstances, the reaction temperature is maintained in the range of 50to 100 C. for 10 to 30 minutes, and 10 to 15 minutes at 80 to 100 C.

The process of the invention, denoted on the chart as Reaction C, isgenerally conducted by reacting the tricyclic hemi-ketal product ofReaction B with a phosphorous halide, such as phosphorous pentachlorideor phosphorous pentabromide. At least about one mole of phosphorushalide is employed per mole of hemi-ketal, but an excess can be employedif desired, for example, up to ten moles per mole. A solvent can beemployed for the process. The hemi-ketal compound starting material ismixed with the phosphorus pentahalide and heated slowly withagitation-The reaction is exothermic and evolves hydrogen halide gas.After the initial mixing step, the reaction mixture is ordinarily heatedat the reflux temperature or generally in the range of 100 to 150 C. fora period of about 1 to 5 hours. The reaction product is hydrolyzed bycontacting with at least one mole of water per mole of product, althougha large excess of water is generally employed. Thereafter the productcan be purified by recrystallization, washing, drying, and othersuitable methods.

The bicyclic ketone product of the invention is capable of undergoing anumber of interesting reactions. The ketone of the invention can bereacted with an alkoxide of the type described with respect to ReactionA to form the ketal product which bears a R Z radical, i.e., of the typeproduced in Reaction A. Moreover, the bicyclic ketone of the inventioncan be reacted with an alkali metal bicarbonate, such as a bicarbonateof sodium, potassium, rubidium or cosium tofogn al eni ketal producthaving a hydroxyl radical, i.e., of the type produced in Reaction B. Thelatter reaction is preferably carried out by contacting a mixture of thebicyclic ketone, the desired alkali metal bicarbonate, water, and analcohol diluent of the formula R ZH described hereinbefore. The mixtureis heated, preferably at the reflux temperature, although temperaturesin the range of 50 to 150C. can be used. The reaction time can vary fromas little as an hour up to 10 to l5 hours. After the completion of thereaction, the alcohol diluent can be removed by distillation, and theproduct can be purified by phase separation, washing, drying, and othersuitable methods.

In another reaction, the bicyclic ketone of the invention is contactedwith an alkali metal cyanide, such as a cyanide of sodium, potassium,lithium, rubidium or cesium. At least one mole of cyanide is generallyemployed per mole of bicyclic ketone, but an excess, up to 10 moles permole can be employed. The reaction is generally carried out by addingthe'alkali metal cyanide to a solution of the bicyclic ketone dissolvedin an alcohol of the formula R ZH described hereinbefore. The reactionmixture is heated to an elevated temperature, generally in the range ofabout 50 to 150 C., and preferably at about the reflux temperature ofthe mixture for a period of l to 10 hours. The resulting reactionproduct can be acidified with a dilute mineral acid such as sulfuricacid, hydrochloric acid, and the like. The reaction diluent can 'beremoved by distillation and the resulting product can be purified bycrystallization, washing, drying, and other suitable methods.

The bicyclic ketone of th invention can also be reacted with compoundssuch as the alkali metal thiocyanaics, e.g., potassium thiocyanate; andalkali metal azides, e.g., sodium aside, to provide products having thecorresponding nucleophilic radicals attached to the 30 bicyclic nucleus.For those reactions, the conditions are similar to those employed withreactants such as the alkali metal cyanides.

The various products of the above-described reactions can be reactedwith halogens and halogen halides to produce compounds wherein thehydrocarbyl, e.g., alkyl, cycloalkyl, alkenyl and aryl substituents asrepresented by X, X X, X, R, R, R R and R are converted to thecorresponding halogen-substituted radicals as represented by X, X X, X,R, R R, R and R respectively. R represents the same radicals as R and inaddition, halogen-substituted alkyl and halogen-substituted cycloalkyl.The resulting halogensubstituted alkyl, alkenyl, cycloalkyl and arylradicals are as described hereinbefore.

The tricyclic compounds disclosed herein are disclosed and claimed inco-pending U.S. Pat. application Ser. No. 413,947, filed on even dateherewith now US. Pat. No. 3,346,596.

The following examples illustrate the invention, but,

are not intended to limit it. All parts are by weight, all

analyses are given in percentage by weight, and temperatures are givenin degrees Centigrade, unless indicated otherwise.

EXAMPLE 1 PREPARATION OF 4-ETHOXY-5,6,7,7,8-PENTACHLORO-3-oxatricyclo-[4.2.l.0- NONANE (REACTION A) Calculated hydroxyl no.: 151;found: 149

ter, washed several times with water and dried under vacuum at 50 C.overnight to a constant weight of 332 parts. Recrystallization fromn-heptane and a treatment with activated charcoal yielded 325 parts ofproduct, having a melting point of 110 to lll.5 C. Product analysis was:I

Calculated for C H O Cl z Cl, 52.1; C, 35.3; H, 3.24

Found: Cl, 52.0; C, 35.4; H, 3.36

EXAMPLE 2 PREPARATION OF 4-ETHOXY-9-HYDROXYMETHYL-S,6,7,7,8-PENTACHLORO-3-OXATRICYCLO [4.2. 1 .0 NONANE (REACTION A) A reactionvessel equipped with an agitator and a condenser was charged with 1,177parts of anhydrous ethanol. To this alcohol was added portionwise 92parts of sodium metal. The resulting solution was agitated at reflux anda solution of 361 parts of- 1,4,5,6,7,7-

with water, filtered, dried, and recrystallized from nhexane to give 240parts of crystals, having a melting point of 138.5 to 140 C. Anotherrecrystallization raised'themelting point to 140.5 to 141.5 C. Theproduct analyzed as follows:

Calculated for c n cgo C, 35.67; H, 3.51; C1, 47.86 I I Found: C, 35.78;H, 3.54; CI, 47.78

I ExAivtPLE 3 PREPARATION OF 9-CHLOROMETHYL4-ETHOXY-5,6,7,7,8-PENTACHLORO-3-OXATR1CYCLO 4.2. 1 .0 NONANE which required six hours.Thereaction mixture was cooled and poured into ice. The oily solidproduct resulting was trituratedwith water, then taken up in nhexane.After washing the resulting hexane solution with water, drying over CaSOfiltering and cooling to C., the hexane solution gave 13.3 parts ofsolid product having a melting point of 86. 5. to 87.5 C. 1n-

frared'analysis of the product showed the product was not unsaturatedand contained no carbonyl or hydroxyl groups. Chemical analysis of theproduct showed:

Calculated. for C H o' Cl CI, 54.7; C, 33.97; H,

3.1 1 I I Found: Cl, 55.1; C, 34.16; H, 2.93

EXAMPLE 4 PREPARATION OF 7,7-DIMETHOXY-4-ETI-IOXY-5,6,8-TRICHLORO-3-OXATRICYCLO-[4.2.1.0]NONANE (REACTION A) To 118 parts of anhydrousethanol were added 10.2 parts of metallic sodium. This solution waswarmed to reflux with agitation, and a solution of 32.2 parts of 1.4-,5,6-tetrachloro-2-hydroxymethyl-7,7-dimethoxybicyclo( 2.2. 1 )-heptenewas added over a period of 0.75 hours. The suspension was stirred forthree hours at rcflux, then filtered and the solvent was stripped. Theresidue was treated with excess water, and the resulting suspension wasacidified with hydrochloric acid. The resulting oil solidified and wasrecrystallized from about 96 parts by weight of petroleum ether immersedin a dry ice-acetone cooling bath. The white solid product weighing 24.0parts had a melting point of 62 to 68 C. and was recrystallized to yield20.0 parts by weight of product having a melting point of 68.5 to 695 C.Analysis of the product showed:

Calculated for C H Cl O C, 44.10; H,.5.24; CI,

Found: C, 43.60; H, 5.14; CI, 32.19

Using the same procedure, the compounds 1,4,5,6- tetrachloro2-hydroxymethyl-7,7-dibromobicyclo(2.2. 1 )-5-heptene andl,4,5,6-tetrachloro-2- hydroxymethyl-7,7-difluorobicyclo( 2.2. 1)-5-heptene are reacted to produce 7,7-dibromo-4-ethoxy-5,6,8-trichloro-3-oxatricyclo[4.2.1.0"]nonane and 7,7-difluoro-4-ethoxy-5,6,8-trichloro-3-oxatricyclo[4.2. l .0 ]nonane,respectively.

EXAMPLE 5 PREPARATIONOF 4-I-IYDROXY-5,6,7,7,8-PENTACHLORO-3-OXA-TRICYCLO-[4.2.1.0%]NONANE (REACTION B) A suspension of 30 parts of4-ethoxy-5,6,7,7,8- pentachloro-3-oxatricyclo[4.2.1.0 ']nonane in 92parts .by weight of concentrated sulfuric acid was warmed to 88 to 100C. with stirring and was held for 0.75 hour. The hot acidsolution waspoured into 700 parts of ice and water, and the resulting suspension waswarmed to C., then cooled and filtered. Then 13 parts of solid productwere recrystallized from benzene EXAMPLE 6 PREPARATION OF4-HYDROXY-9-HYDROXYMETHYL-S,6,7,7,8- PENTACHOLORO-3-OXATRICYCLO[4.2.1 .0'v

]NONANE (REACTION B) -A suspension of 221 parts by weight ofconcentrated sulfuric acid and 24 parts of 4-ethoxy9-hydroxymethyl-S,6,7,7,8-pentachloro-3-oxatricy clo[4.2.1.0*' ]rionanewith concentrated sulfuric acid was stirred with heating to 90 to 92 C;and held at this temperature for eight minutes. The resulting solutionwas poured into ice and the solid collectedon a filter.

lowing results After a thorough washing with water, 15 parts of solidproduct ware recrystallized three times from methanol and water to yield10.8 parts of solid product having a melting point of 236 to 238 C.Infrared analysis showed the presence of the carbonyl and hydroxylbroups.

Elemental analysis of the product showed:

Calculated for C H Cl O C, 1.58; H, 2.63; CI, 52.2

Found: c, 31.81; H, 2.61; ct. 52.0

EXAMPLE 7 PREPARATION OF 9-CHLOROMETHYL-4-HYDROXY-S,6,7,7,8-

PENTACHLORO- l -OXATRICYCLO [4.2.1.0 ]NONANE (REACTION B)- 25 parts of4-ethoxy-9-chloromethyl-5,6,7,7,8- pentachloro-3-oxatricyclo[ 4.2. 1.0"]nonane were added to l 10 parts by weight of concentrated sulfuric acidover a period of minutes while stirring the mixture. The resultingsuspension was heated to 94 C. and

held at that temperature for 20 minutes, and was then cooledby pouringonto ice. 23 parts of a white solid product were isolated from thereaction mixture. The product was recrystallized from benzene and 17parts of product were recovered having a melting point of l44.5 to 146C. Example analysis of the compound gave the following results:

Calculated for C H Cl O C, 29.95; H, 2.23; Cl,

lowing reactants to give the indicated products.

Calculated for C H Cl O C, 29.05; H, 1.83; CI, 64.3

Found: c, 2923,11, 197; C1, 63.80

EXAMPLE 9 PREPARATION OF Z-KETO-S,6?B1S(CHLOROMETHYL)-1.3.4.7,7-

PENTACHLOROB1CYCLO(2.2. 1')HEPTANE (REACTION c) A mixture of 100 partsof 9-chloromethyl-4-hydroxy- 5 ,6,7,7,8-pentachloro-3-oxatricycle[4.2. l.O ]n0nane and 74 parts of phosphorus pentachloride was heated slowly tothe reflux temperature. An exothermicreaction took place, accompanied byevolution of hydrogen chloride. The reaction mixture was refluxed at 136C. for 1.5 hours. The resulting reaction product was poured into waterand washed thoroughly and then extracted with hexane. The reactionproduct was dried in contact with magnesium sulfate and then the hexanesolvent was distilled off. The product distilled at a temperature of 140to 144 C. and 1 mm. mercury. Infrared analysis of the product indicatedthe presence of the carbonyl group. Chemical analysis gave the followingresults:

Calculated for C H Cl O: C, 28.57; H, 1.60; CI, 65.6

' Found: C, 28.32; H, 1.66; CI, 68.2

Additional compounds of the invention are readily produced using themethod of Example 9'with the fol- EXAMPLE HEMI-KETAL REACTANT HALIDEPHOSPHORUS M PRODUCT Found: c, 30.18; H, 2.23; c1, 58.5

EXAMPLE 8 PREPARATION OF v 2-KETO-6-CHLOROMETHYL-l ,3,4,7,7-PENTA-'CHLOROBICYCLO-(2.2. l HEPTANE (REACTION A mixture of 187.4 parts of4-hydroxy-5,6,7,7,8- pentachloro-3-oxatricyclo[4.2. l .O" ]nonane. and146 parts of phosphorus pentachloride' was carefully warmed withagitation. At C., an exothermic reaction took place with vigorousevolution of hydrogen chloride. The pale yellow, resulting solution wasstirred at reflux (118120 C.) for 2 hours, then poured into crushed ice.The white solid obtained was washed several times with water andrecrystallized from hexane to yield 110 parts of product having amelting point of 69.5 to 71.5 C. Analysis of the product gave the fol-PREPARATION OF 4-METHOXY-5,6,7,7,8-PENTACHLORO-3- OXATRICYCLO [4.2. l .O]NONANE Over a period of a few minutes, 100 parts of 2-keto-6-chl0romethyl-l ,3 ,4,7,7-pentachlorobicyclo(2.2.1- )heptane were addedto 1,570 parts by weight of a solu;

tion prepared by adding 25 parts of sodium to methyl alcohol at reflux.The resulting dark suspension was refluxed for 12 hours. Then the excessmethanol was distilled from the product under vacuum, and the residuewas acidified and filtered. The filter cake was washed with water and 60parts of solid product were recovered and recrystallized from heptane toprovide a product having a melting point of 82 to 85 C. The meltingpoint indicated the product to be the same as that produced using theprocedure of Examplgl with metah nol prostrate at 24 hours).

as the solvent. The product was also analysed by infrared analysis, andthe resulting spectrum was the same as that of the product producedusing the procedure of Example 1 with methanol asthe solvent.

EXAMPLE l4 PREPARATION OF 4-HYDROXY- ,6,7,7,8-PENTACHLORO:3-OXATRICYCLO-[4.2.1.0 ]NONANE EXAMPLE l5 PREPARATION OF 4-CYANO-5,6,7,7,8-PENTACHLORO-3- OXATRICYCLO- [4.2.l.0"' ]NONANE A solutioncontaining 132 parts of 2-keto-5,6- bis(chloromethyl)-1,3,4,7,7-pentachlorobicyclo(2.2. 1-. )heptane in 785 parts by weight ofethanol and parts by Weight of water was treated with 52 parJs ofpotassium cyanide. The solution was stirred at reflux for 2.0 hours. Theresulting dark suspension was acidified with dilute sulfuric acidandthen evaporated to near dryness. The residue was poured into water andthe brown solid collected on a filter. The solid was dissolved inhexane, dried over magnesium sulfate (anhydrous), and filtered. Theexcess hexane was removed, and crystals separated upon chilling thesolution. 60 parts of product were recovered having a melting point of226 to 231 C. Recrystallization raised the melting point fo 235 to 236C. Elemental analysis of the product gave the following results:

Calculated for c u oivcu; c, 33.63; H, 1.88; N;

4.36; C], 55.16 Found: C, 33.7; H, 2.02; N, 4.28; Cl, 54.98

EXAMPLES 16 to 17 I Aqueous dispersions of certain of the compounds ofthe invention wereprepared. These dispersions at the concentration of 1%were sprayed onto houseflies (musca domestica) and the number ofprostrate flies was counted at 2 and 24 hours (considered dead ifPROSTRATE DEAD AT EXAMPLE NO. COMPOUND AT 2 HOURS 24 HOURS .O' CHgCl.listed by Kenaga, Bull.

'by Kenaga (loc.cit., pg. 69,70,92). 'Oth er adjuvants 14 In theforegoing examples. the components have been named in accordance withthe system ol nomcn claturc employed by Chemical Abstracts, and with theprovision that the compounds have the following struc .tural formula:

wherein the numerals indicate the position of substituents attached .tothe tricyclic nucleus. Thus, the ompound prepared in Example 2 has beennamed 4- ethoxy-9-hydroxymethyl-5,6,7,7,.8-pentachloro-3- oxatricyclo[4.2. l .0 ]nonane. Attachment of the oxygen to a different position onthe initial bicyclic structure to provide the following structuralfomula: V g

requires renumbering some of the positions of the tricyclic structure,as indicated by the numerals. Under these circumstances, the compoundproduced in Example 2 is named 4-ethoxy-8-hydroxymethyl-5,6,6,7,-.'

nated arylsulfonates, chlorinated diarylsulfones and the like,fungicidessuch as sulfur, dithiocarbamates and N-trichloromethylthio-4-cyclohexenel ,2-dicarboximide to list but a few.Other insecticides with which the compounds of the invention can beemployed are those Ent. Soc. 'America, 9, 69 ft (1963). I

It may also be desirable to combine the insecticidal products of thisinvention with a class of potentiators or synergists known in theinsecticidal art as knockdown agents. Among the large number ofsynergists and knockdown agentswhich can be used for this purpose arethe organic thiocyanates and others listed useful with the compounds ofthe invention include odorants, colorants, stabilizers, and extendingagents (vapor pressure depressants and nonvolatile solvent substancessuch as chlorinated waxes, resins, and the like).

Another advantage of the inventive compositions is that they may readilybe formulated as solids or liquids using solid or liquid solventvehicles. carriers. or extenders. Suitable diluents are solids orliquids of an inert nature. Illustrative solid diluents include amongmany others: sawdust, vermiculite, clay, talcs, flours, silicas,alkaline earth carbonates, oxides and phosphates, solid fertilizer, andthe like. Suitable solvents for liquid formulations include ketones,aromatic and aliphatic hydrocarbons and petroleum fractions ordistillates such as xylenes, aromatic naphthas, and the like.

Whether dissolved or dispersed, suspended or emulsified in a liquid orformulated as a dust or powder or some other solid preparation theinsecticides of this invention can advantageously contain one or moresubstances known or referred to variously as modifiers, wetting agents,or surface-active agents. Suitable agents are alkylaryl sulfonates,polyoxyethylene polyol ethers and cators, and the like.

The compounds of the invention can also be formulated in baitcompositions, for example with fatty, sugary, or proteinaceousingestible bait substances.

For controlling pests the compounds of the present invention are appliedin insecticidal quantities or effective amounts onto the site of theexisting or anticipated harmful pests. Effective insecticidalconcentrations are in the range of from about 0.01 pound per acre toabout 20 pounds per acre. In most crop applications rates of 0.05 topounds per acre are employed. Lower ratesare used on very susceptiblespecies, while higher rates are used on extremely resistant species.Higher rates than pounds per acre may be used where economics permit.

The rate to be used depends on many variables such as the insectspecies, duration of control desired, weather, soil type, crop species,timing between application and harvest, economics and other factorsknown to one of skill in this art. The application of the insecticidecan be to the crop itself or to the soil in which it is grown.

While this invention has been described with reference to certainspecific embodiments, it will be recognized by those skilled in the artthat many variations are possible without departing from the spirit andscope of the invention.

What is claimed is:

l. A compound of the formula R and R are independently selected from thegroup consisting of hydrogen, lower alkyl, monohalo lid lower alkyl,phenyl, monochlorophenyl, cyclohexyl and monochlorocyclohexyl; and R andR can join to form a cycloalkyl group of 5 to 8 carbon atoms. 2. Thecompound according to claim 1 having the formula wherein;

X and X are independently selected from the group consisting ofhydrogen, halogen, lower alkyl and lower alkenyl;

X and X are halogen;

X is independently selected from the group consisting of hydrogen andhalogen; 1

X is halogen;

R and R are independently selected from the group I consisting ofhydrogen, chlorine lower alkyl, lower alkenyl, monohalo lower alkyl andmonohalo lower alkenyl;

R and R are independently selected from the group consisting ofhydrogen, lower alkyl, monohalo lower alkyl, cyclohexyl andmonochlorocy- .clohexyl; and

R and R can join to form a cycloalkyl group of 5 to 8 carbon atoms.

4. The compound according to claim 3 of the formula wherein;

R and R are independently selected from the group consisting ofhydrogen, chlorine lower alkyl, lower alkenyl, monohalo lower alkyl, andmonohalo lower alkenyl, and wherein; I R and R are independentlyselected from the group X", X, X, X", X", R", R R and R have theconsisting of hydrogen, lower alkyl, monohalo meaning recited herein;and.

lower alkyl, cyclohexyl, and monochlorocy- X is halogen.

clohexyl. 5 7. A process which comprises reacting at a tempera- 5. Acompound having the formula: ture of from about 100 C to about refluxphosphorus pentachloride with a compound having the formula;

I Cl

- H II OHCI or f onion H Ch 7 B0 -II 6. A process which comprisesreacting at a temperature of from about 100 C to about reflux aphosphorus l pentahalide with a compound having the formula:

Xll n i N mum H l Rn and thereafter washing with water the reactionproduct XHJ @N I 20 to produce'- the compound having the formula;

X" i Cl nz-K H r i v H H X12 o1 GHlCl 0 R13 C012 1!! O CHrCl wherein; I1

X" and X are independently selected from the group consisting ofhydrogen, halogen, lower alkyl 8. A process which comprises reacting ata temperad l e lk l; ture from about 100 C to about reflux phosphorus Xand X are halogen; pentachloride with a compound having the formula; Xis independently selected from the group consisting of hydrogen andhalogen; 01

R and R are independently selected from the group consisting ofhydrogen, chlorine lower alkyl, H lower alkenyl, monohalo lower alkyl,and mono- C1 001 halo lower alkenyl; HO R and R are independentlyselected from the group consisting of hydrogen, lower alkyl, mono- 40 I6 halo lower alkyl, phenyl, monochlorophenyl, cy- O 1 H clohexyl, andmonochlorocyclohexyl;

Z is independently selected from the group consisting of Oxygen andSulfur; and thereafter washing with water the reaction product and thenwashing with water the reaction product to to P 9 319 9 h v gth f m lproduce a compound having the formula UNITED STATES PATENT OFFICE 569CERTIFICATE OF CORRECTION Patent No. a 7 D t d June 28,, 1974Inventor(s) Paul E. Hoch It is certified that error appears in theabove-identified patent and that said Letters Patent are herebyCorrected as shown below:

r- In Title Page under "related U.S, Application data" line 2, "31969" 1should read 1968 after "3,661,998" insert issued May 9, 1972, Title pageunder "ABSTRACT" 3rd line from bottom of Abstract, "yricyclic" shouldread tricyclic Column 2, line 2, "chlorodedecy'l" should readchlorododecyl line 31, "chlorocyclohoxyl" should read chlorocyclohexylline 3 5, "elkyl" should read --alkyl Column 3, first formula left handside,' that portion of the structural formula reading "CH-CHCl" shouldread CH=CHCl Column 5, line 53, "3-hy'droxycyclopentene," should read3-hydroxycyclopentene-l, line 53, "4,-B-hydroxycyclohexene- 1," shouldread -J- B-hydroxycyclohexene-l, Column 7, line 60, "cosium" should readcesium Column 8, line 25, "th" should read the line"2T6,"thiocyanaics"should read thiocyanates line 28, "aside" should read azide Column 9 ine47, "4-othoxy" should read 4-ethoxy line 48, /4.2.1.o 3 should read4..2.1.0 Column 10, line 59;, "PENTACHOLORO" should read PENTACHLOROColumn 11, line 5, "broup s" should read groups line 27, "Example"should I read Elemental line 61, "At 50C. shoiild read At 50 to 55C,Column 12, line 11, "tricycle" should read tricyclo Columns ll and 12Table, "HALIDE" should read PHOSPHORUS HALIDE heading "PHOSPHORUSPRODUCT" should read PRODUCT --a Column 12, last line "metahnol" shouldread methanol Column 13, line 18, "insuluble" should read insoluble line31, "parJs" should read parts line 41, "f0" should read to Column 14,lines 16 and 17, "ompound" should read compound line 35,"-5,6,6,7,-pentachloro" should read ---5,6,6,7,9-pentachloro line 45,"lindene" should read lindane Column 15, line 16, "cators" should readesters Column 16, I line 3, Claim 1, "R should read line 44, Claim 3,"chlorine lower" should read chlorine, lower line 66, Claim 4, "chlorinelower" should read chlorine, lower Column 17, line 36, Claim 6,"chlorine lower" should read I--- chlorine, lower Signed and sealed this4th day of February 1975.

(sEAL) Attest:

McCoy M. GIBSON JR. 0. MARSHALL DANN Arresting Officer Commissioner ofPatents

2. The compound according to claim 1 having the formula
 3. A compound ofthe formula
 4. The compound according to claim 3 of the formula
 5. Acompound having the formula:
 6. A process which comprises reacting at atemperature of from about 100* C to about reflux a phosphoruspentahalide with a compound having the formula:
 7. A process whichcomprises reacting at a temperature of from about 100* C to about refluxphosphorus pentachloride with a compound having the formula;
 8. Aprocess which comprises reacting at a temperature from about 100* C toabout reflux phosphorus pentachloride with a compound having theformula;